RU2013122565A - POLYETHYLENE AND METHODS OF ITS PRODUCTION - Google Patents

POLYETHYLENE AND METHODS OF ITS PRODUCTION Download PDF

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RU2013122565A
RU2013122565A RU2013122565/04A RU2013122565A RU2013122565A RU 2013122565 A RU2013122565 A RU 2013122565A RU 2013122565/04 A RU2013122565/04 A RU 2013122565/04A RU 2013122565 A RU2013122565 A RU 2013122565A RU 2013122565 A RU2013122565 A RU 2013122565A
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solution
methylaluminoxane
copolymer
trimethylaluminum
transition metal
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RU2013122565/04A
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RU2592276C2 (en
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Донна Дж. КРАУТЕР
Дейвид М. ФИСКУС
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Эксонмобил Кемикэл Пейтентс Инк.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged

Abstract

1. Способ полимеризации олефинов, включающий взаимодействие одного или большего количества олефинов с каталитической системой, содержащей металлоценовое соединение переходного металла и раствор метилалюмоксана, в способе количество триметилалюминия в растворе метилалюмоксана устанавливают равным от 1 до 25 мол.% или от 1 до 25 мас.% до использования в качестве активатора, где содержание триметилалюминия в мол.% или мас.% определяют с помощьюН ЯМР раствора до объединения с любой подложкой.2. Способ полимеризации олефинов, включающий взаимодействие одного или большего количества олефинов с каталитической системой, содержащей металлоценовое соединение переходного металла и раствор метилалюмоксана, и в этом способе количество неизвестных соединений, содержащихся в растворе метилалюмоксана, устанавливают равным от 0,10 до 0,65 интегральных единиц на основании пика триметилалюминия, нормированного на 3,0 интегральные единицы, до использования в качестве активатора, где неизвестные соединения идентифицируют, как третий сигнал вН ЯМР спектре раствора до объединения с любой подложкой в дополнение к сигналу, относящемуся к олигомерному метилалюмоксану, и сигналу, относящемуся к триметилалюминию, где указанные три сигнала, указанные в настоящем изобретении, не включают сигналов какого-либо растворителя.3. Способ по любому из пп.1 или 2, в котором количество триметилалюминия и количество неизвестных частиц регулируют путем добавления или удаления триметилалюминия, предпочтительно путем добавления или триметилалюминия в раствор метилалюмоксана или его удаления из раствора.4. Способ по любому из пп.1 или 2, в котором кат1. The method of polymerization of olefins, including the interaction of one or more olefins with a catalytic system containing a metallocene compound of a transition metal and a solution of methylaluminoxane, in the method the amount of trimethylaluminum in a solution of methylaluminoxane is set equal to from 1 to 25 mol.% Or from 1 to 25 wt.% before use as an activator, where the content of trimethylaluminum in mol.% or wt.% is determined using N NMR solution before combining with any substrate. 2. A method for the polymerization of olefins, comprising reacting one or more olefins with a catalyst system containing a metallocene transition metal compound and a methylaluminoxane solution, and in this method, the number of unknown compounds contained in the methylaluminoxane solution is set from 0.10 to 0.65 integral units per based on a trimethylaluminum peak normalized to 3.0 integral units, before being used as an activator, where unknown compounds are identified as the third signal in NMR spectrum of the solution prior to combining with any substrate in addition to the signal relating to the oligomeric methylaluminoxane and signals relating to trimethylaluminum, wherein said three signals mentioned in the present invention does not include any signal rastvoritelya.3. The method according to any one of claims 1 or 2, wherein the amount of trimethylaluminum and the amount of unknown particles are controlled by adding or removing trimethylaluminum, preferably by adding or trimethylaluminum to the solution of methylaluminoxane or removing it from the solution. The method according to any one of claims 1 or 2, wherein

Claims (15)

1. Способ полимеризации олефинов, включающий взаимодействие одного или большего количества олефинов с каталитической системой, содержащей металлоценовое соединение переходного металла и раствор метилалюмоксана, в способе количество триметилалюминия в растворе метилалюмоксана устанавливают равным от 1 до 25 мол.% или от 1 до 25 мас.% до использования в качестве активатора, где содержание триметилалюминия в мол.% или мас.% определяют с помощью 1Н ЯМР раствора до объединения с любой подложкой.1. The method of polymerization of olefins, including the interaction of one or more olefins with a catalytic system containing a metallocene compound of a transition metal and a solution of methylaluminoxane, in the method the amount of trimethylaluminum in a solution of methylaluminoxane is set equal to from 1 to 25 mol.% Or from 1 to 25 wt.% before use as an activator, where the content of trimethylaluminum in mol.% or wt.% is determined using 1 H NMR solution before combining with any substrate. 2. Способ полимеризации олефинов, включающий взаимодействие одного или большего количества олефинов с каталитической системой, содержащей металлоценовое соединение переходного металла и раствор метилалюмоксана, и в этом способе количество неизвестных соединений, содержащихся в растворе метилалюмоксана, устанавливают равным от 0,10 до 0,65 интегральных единиц на основании пика триметилалюминия, нормированного на 3,0 интегральные единицы, до использования в качестве активатора, где неизвестные соединения идентифицируют, как третий сигнал в 1Н ЯМР спектре раствора до объединения с любой подложкой в дополнение к сигналу, относящемуся к олигомерному метилалюмоксану, и сигналу, относящемуся к триметилалюминию, где указанные три сигнала, указанные в настоящем изобретении, не включают сигналов какого-либо растворителя.2. A method for the polymerization of olefins, comprising reacting one or more olefins with a catalyst system containing a metallocene transition metal compound and a methylaluminoxane solution, and in this method, the number of unknown compounds contained in the methylaluminoxane solution is set to be from 0.10 to 0.65 integral units based on a peak of trimethylaluminum normalized to 3.0 integral units before being used as an activator, where unknown compounds are identified as the third signal in the 1 H NMR spectrum of the solution prior to combining with any substrate in addition to the signal related to oligomeric methylaluminoxane and the signal related to trimethylaluminum, where the three signals indicated in the present invention do not include signals of any solvent. 3. Способ по любому из пп.1 или 2, в котором количество триметилалюминия и количество неизвестных частиц регулируют путем добавления или удаления триметилалюминия, предпочтительно путем добавления или триметилалюминия в раствор метилалюмоксана или его удаления из раствора.3. The method according to any one of claims 1 or 2, in which the amount of trimethylaluminum and the number of unknown particles are controlled by adding or removing trimethylaluminum, preferably by adding or trimethylaluminum to the solution of methylaluminoxane or removing it from the solution. 4. Способ по любому из пп.1 или 2, в котором каталитическая система в растворе метилалюмоксана до объединения с любой подложкой характеризуется отношением количества молей алюминия к количеству молей переходного металла (предпочтительно отношением количества молей алюминия к количеству молей гафния), составляющим 175:1 или менее.4. The method according to any one of claims 1 or 2, in which the catalytic system in a solution of methylaluminoxane prior to combining with any substrate is characterized by the ratio of the number of moles of aluminum to the number of moles of transition metal (preferably the ratio of the number of moles of aluminum to the number of moles of hafnium) of 175: 1 or less. 5. Способ по любому из пп.1 или 2, в котором металлоценовое соединение переходного металла описывается формулой:5. The method according to any one of claims 1 or 2, in which the metallocene transition metal compound is described by the formula: CpACpBHfX∗n Cp A Cp B HfX ∗ n в которой каждый X∗ и каждая группа Cp химически связана с Hf, n равно 1 или 2, CpA и CB могут быть одинаковыми или разными циклопентадиенильными лигандами или лигандами, изолобальными по отношению к циклопентадиенилу, любой из которых или оба могут содержать гетероатомы и любой из которых или оба могут быть замещенными, и где способ предпочтительно является газофазным способом.in which each X ∗ and each Cp group is chemically bonded to Hf, n is 1 or 2, Cp A and C B can be the same or different cyclopentadienyl ligands or ligands, isobalic to cyclopentadienyl, either of which can contain heteroatoms and either of which or both may be substituted, and where the method is preferably a gas phase method. 6. Способ влияния на меж- и/или внутримолекулярное распределение сомономера и/или молекулярно-массовое распределение в сополимере путем регулирования количества триметилалюминия в каталитической системе, использующейся в способе полимеризации, каталитическая система включает раствор метилалюмоксана и металлоценовое соединение переходного металла.6. A method for influencing the inter- and / or intramolecular distribution of the comonomer and / or molecular weight distribution in the copolymer by controlling the amount of trimethylaluminium in the catalyst system used in the polymerization method, the catalyst system includes a methylaluminoxane solution and a transition metal metallocene compound. 7. Способ по п.6, в котором в сополимере содержание триады ([ННН]) сомономера увеличивают и/или молекулярно-массовое распределение уменьшают путем уменьшения количества триметилалюминия в каталитической системе, содержащей раствор метилалюмоксана и металлоценовое соединение переходного металла, где Е означает образованное из этилена звено и H означает образованное из сомономера звено в сополимере.7. The method according to claim 6, in which in the copolymer the content of the triad ([IUU]) of the comonomer is increased and / or the molecular weight distribution is reduced by reducing the amount of trimethylaluminum in a catalyst system containing a solution of methylaluminoxane and a metallocene transition metal compound, where E means formed from ethylene, and H means a unit formed from a comonomer in a copolymer. 8. Способ улучшения рабочих характеристик пленки, предпочтительно сопротивления раздиру и/или ударопрочности пленки, изготовленной из сополимера этилена, путем уменьшения количества триметилалюминия в каталитической системе, использующейся в способе полимеризации, каталитическая система включает раствор метилалюмоксана и металлоценовое соединение переходного металла.8. A method for improving film performance, preferably tear resistance and / or impact resistance of a film made from an ethylene copolymer by reducing the amount of trimethylaluminium in the catalyst system used in the polymerization method, the catalyst system includes a methylaluminoxane solution and a transition metal metallocene compound. 9. Способ по любому из пп.6-8, в котором способом полимеризации является непрерывным способ, предпочтительно газофазный способ, и количества триметилалюминия регулируют в реальном масштабе времени до поступления в реактор полимеризации.9. The method according to any one of claims 6 to 8, in which the polymerization method is a continuous method, preferably a gas phase method, and the amounts of trimethylaluminium are adjusted in real time before entering the polymerization reactor. 10. Способ мониторинга количества триметилалюминия в каталитической системе, использующейся в способе полимеризации, каталитическая система включает раствор метилалюмоксана и металлоценовое соединение переходного металла, путем мониторинга интенсивности (посредством интегральных единиц) сигнала 1Н ЯМР неизвестных частиц, содержащихся в растворе метилалюмоксана, и этот сигнал является третьим сигналом в 1Н ЯМР спектре раствора до объединения с любой подложкой в дополнение к сигналу, относящемуся к олигомерному метилалюмоксану, и сигналу, относящемуся к триметилалюминию, где указанные три сигнала, указанные в настоящем изобретении, не включают сигналов какого-либо растворителя.10. A method for monitoring the amount of trimethylaluminium in the catalyst system used in the polymerization method, the catalyst system includes a methylaluminoxane solution and a transition metal metallocene compound by monitoring the intensity (by integral units) of the 1 H NMR signal of unknown particles contained in the methylaluminoxane solution, and this signal is the third signal in the 1 H NMR spectrum of the solution prior to combining with any substrate in addition to the signal related to oligomeric methylaluminoxane and nalum related to trimethylaluminum, where the three signals indicated in the present invention do not include the signals of any solvent. 11. Сополимер, полученный способом по любому из пп.1-5 или способом по любому из пп.6-9.11. The copolymer obtained by the method according to any one of claims 1 to 5 or by the method according to any one of claims 6 to 9. 12. Сополимер по п.11, которым является сополимер, содержащий этилен и от 0,5 до 25 мол.% C3-C20-олефинового сомономера, указанный сополимер обладает следующими характеристиками: растягивающее напряжение при вторичном пределе текучести, равное 12 МПа или более; отношение предельного относительного удлинения к разрывному напряжению, равное 20 или более; растягивающее напряжение при удлинении на 200% (МПа), которое больше, чем растягивающее напряжение при вторичном пределе текучести (МПа); содержание триад сомономера (триад [ННН]), равное 0,0005 мол.% или более; плотность, равная 0,910 г/см3 или более, и 1% секущий модуль упругости, равный от 30 до 100 МПа.12. The copolymer according to claim 11, which is a copolymer containing ethylene and from 0.5 to 25 mol% of a C 3 -C 20 olefin comonomer, said copolymer has the following characteristics: tensile stress at a secondary yield strength of 12 MPa or more; a ratio of ultimate elongation to tensile stress of 20 or more; tensile stress at elongation of 200% (MPa), which is greater than tensile stress at a secondary yield strength (MPa); the content of triads of comonomer (triads [IUU]) equal to 0.0005 mol.% or more; a density of 0.910 g / cm 3 or more, and a 1% secant modulus of elasticity, equal to 30 to 100 MPa. 13. Сополимер по любому из пп.11 или 12, в котором отклонение от статистического, если статистическое значение мольной доли [ННН] в сополимере вычитают из измеренного значения мольной доли [ННН], больше 0, и/или отклонение от статистического, если статистическое значение мольной доли [ЕНЕ] в сополимере вычитают из измеренного значения мольной доли [ЕНЕ], больше 0.13. The copolymer according to any one of paragraphs.11 or 12, in which the deviation from the statistical, if the statistical value of the molar fraction [IUU] in the copolymer is subtracted from the measured value of the molar fraction [IUU], is greater than 0, and / or the deviation from the statistical if statistical the molar fraction [ENE] in the copolymer is subtracted from the measured molar fraction [ENE], greater than 0. 14. Сополимер по любому из пп.11 или 12, где полимер обладает пределом прочности при растяжении при пределе текучести, равным более 11 МПа, и/или предельным удлинением, равным более 750%, и/или предельным напряжением, равным менее 40 МПа, и/или отношением предельной деформации к предельному напряжению, равным более 17, и/или 1% секущим модулем упругости, равным от 30 до 100 МПа, и/или характеристическим раздиром, равным 300 г/мил или менее.14. The copolymer according to any one of paragraphs.11 or 12, where the polymer has a tensile strength at a yield strength of more than 11 MPa, and / or an ultimate elongation of more than 750%, and / or an ultimate stress of less than 40 MPa, and / or the ratio of ultimate strain to ultimate stress equal to more than 17, and / or 1% secant modulus of elasticity, equal to from 30 to 100 MPa, and / or characteristic shear, equal to 300 g / mil or less. 15. Сополимер этилена с C4-C8-альфа-олефином, содержащий от 0,5 до 25 мол.% сомономера и обладающий плотностью, равной 0,910 г/см или более, в котором отклонение от статистического, если рассчитанное статистическое значение мольной доли [ННН] в сополимере вычитают из измеренного значения мольной доли [ННН], больше 0, и/или отклонение от статистического, если рассчитанное статистическое значение мольной доли [ЕНЕ] в сополимере вычитают из измеренного значения мольной доли [ЕНЕ], больше 0, где Е означает звено, образованное из этилена, и H означает звено, образованное из C4-C8-альфа-олефинового сомономера, в сополимере. 15. A copolymer of ethylene with a C 4 -C 8 alpha-olefin, containing from 0.5 to 25 mol.% Comonomer and having a density equal to 0.910 g / cm or more, in which the deviation from the statistical if the calculated statistical value of the mole fraction [IUU] in the copolymer is subtracted from the measured mole fraction [IUU], greater than 0, and / or a deviation from the statistical if the calculated statistical mole fraction [ENE] in the copolymer is subtracted from the measured mole fraction [ENE], more than 0, where E means a unit formed from ethylene, and H means a unit, formed from a C 4 -C 8 alpha olefin comonomer in a copolymer.
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